Process of dyeing and the dyed materials produced



Patented Aug. 15, 1933 PROCESS OF DYEING AND THE DYED MATERIALS PRODUCEDJoseph Felix Turski, Warsaw, Poland No Drawing. Application July 15,1931, Serial No. 551.041, and in Poland February 14, 1929 27 Claims.

This invention relates to processes of dyeing and the dyed materialsproduced; and it comprises a method wherein a material is impregnatedwith certain intermediates. the impregnated material is treated with adiazotizing means to form a diazo compound in situ and the dyestuif isdeveloped in situ. the intermediate sometimes being simultaneouslydiazotized and selfcoupled to form the dyestufl and it further comprisesmaterials dyed with the dyestuff so produced: all as more fullyhereinafter set forth and as claimed.

In certain priorprocesses, dyestuffs have been developed in a situ in amaterial to bedyed, but in such processes, the fabric was impregnated orpadded with compounds serving as end components only and the impregnatedfabric was treated with a solution of a diazo compound, the diazocompound coupling with the end components to form the dyestuff. In suchprocesses, the diazo compounds, the end components or both weredifferent from the intermediate compounds which are used in my presentprocesses.

I have found that by using certain intermediates containing an aminogroup capable of being diazotized I can impregnate the material to bedyed with said intermediates and diazotize them so that the diazocompound is formed in situ in the material. A dyestuff may then bedeveloped by coupling a suitable end component with the diazo compoundwhich has been formed in situ.

The new intermediates which may be used in my processes are of the typedisclosed and claimed in my prior and copending application. Ser. No.427,068, filed February 8, 1930, of which the present application is acontinuation in part. These intermediates contain an amino group.

They are capable of being diazotized and used as first components inmaking azo dyestuffs. Also they are capable of being coupled with diazocompounds and may be used as end components. Because of these inherentproperties. they may be converted directly into azo dyestuffs withoutthe use of other components: they may be simultaneously diazotized andself-coupled to produce azo dyestuffs in a s. .le step.

In my application Ser. N0.-42"I.068. I have disclosed a class ofintermediates havingthe generic formula:

no -R| v Rte-Nut ll wherein R1 represents an aryl residue or the residueof the enol component of a ketocarbo'xylic wherein R4 representshydrogen or an alkyl group. R6 represents an aryl or alkyl group and R2represents an aryl group. The intermediates in which the R2 represents aresidue of the type may be advantageously used in my processes.

All of these types of intermediates contain an aminogroup capable ofbeing diazotized to give the diazo compounds necessary in my process.Also these intermediates are capable of coupling with diazo compounds toform dyestuffs, acting as end components. When a fabric impregnated withthese intermediates is treated in a diazotizing bath under the properconditions there is both a diazotizing and coupling of the intermediatesto form the dyestuffs in situ.

However other suitable types of compounds may be used for coupling asend components, these end components being applied and coupled after theintermediate has been diazotized in situ to form the diazo compound. Anyof the usual compounds used as end components in making azo dyestuffsmay be coupled in my process with these new intermediate compounds afterthey have been diazotized in situ. Certain compounds disclosed in myprior application Ser. No. 427,068may be likewise used as endcomponents.

For instance compounds of the types having the following probablestructural formula may be used:

ii ii and H-N-Rz- N t i l wherein R1 and R2 represent aryl residues.

Also the intermediates may be used in my process as end components only.the dyestuif in such cases being developed by coupling with a diazocompound. But in this procedure. the shades obtained are not assatisfactory as in the processes set forth ante. However. if thecoupling is made with care and the diazo compounds properly selected.satisfactory shades may be produced by using this modification of mygeneric process. For instance using tetrazotized dianisidin and couplingthe tetra-azo compound under the proper conditions with my newintermediates as end components, satisfactory shades may be obtained,the shade being in most cases a permanent bluish black. The diarninointermediates disclosed in my prior application Ser. No. 427,068 whichmay be represented by the probable structural formula:

wherein R1 and R2 represent aryl residues may be tetra-azotized andcoupled with the new intermediates of the type disclosed which contain ahydroxyl group, to produce the dyestuff.

In my processes. the material to be dyed is first impregnated with thenew intermediate- The fabric may be impregnated by means of an aqueoussolution of the intermediate. Most of these intermediates aresubstantially insoluble in water alone but they dissolve in aqueoussolutions containing a little caustic soda. In some instances theintermediates in the form of the hydrochlorid, that is in the form ofsalts combined with hydrochloric acid or other acids. are soluble inwater and solutions may be prepared. The fabric may be impregnatedeither by means of an aqueous alkaline solution or by solutions of thesaline or hydrochlorid type combinations of the intermediate.

These impregnating baths may be prepared in any suitable manner. Analkaline impregnating bath may be prepared by dissolving theintermediate in an aqueous soda solution, diluting the solution thusobtained with hot water and boiling to clarify the solution which may befiltered if necessary. A clear solution is then diluted with cold waterto give the proper volume and concentration for use in impregnating thematerial to be dyed with the proper amoun f intermediate. For instance.an aqueous solution may be prepared by mixing together say 25 cc of 40B. caustic soda solution and suflicient water to make about 200 cc.About 20' grams of the intermediate may be dissolved in this mixturewhich may be first warmed, advantageously to temperatures between and 90C. The particular amount of intermediate to be dissolved in the mixtureand the exact amount of caustic soda solution used are adjusted to theparticular conditions and the results desired. After the intermediate isadded the mixture is heated to obtain a clear solution. the mixturebeing then diluted with warm water. Conditions are so adjusted as toobtain a clear solution and facilitate filtering to remove insolubleimpurities if they be present. The clear solution may be diluted withcold water to give the proper concentration. The clear solution may ormay not be cooled before final dilution.

In some instances. it is advantageous that the bath contain other addedingredients. For example. it is sometimes advantageous to add Turkey redoil. The intermediate may first be mixed with a proper amount of Turkeyred oil, the mixture stirred into a hot aqueous solution of cansticsoda. at. say. about 80 to 90 C.; the caustic solution containing. say.approximately 30 cc of 30 B. caustic soda to 200 cc hot water. Ihe bathobtained is stirred until the ingredients are thoroughly mixed and isthen diluted with 500 cc of cold water and reheated to obtain a clearsolution. The solution is then cooled and may be further diluted toabout 1 liter with cold water. The ratio of Turkey red oil to theintermediate may be roughly about 1:3. This ratio may be varied with theparticular intermediate and the particular dyeing process in which theimpregnating bath is to be used and the character of the fabric; thespecific steps of dyeing being of course given due consideration.

The impregnating bath may also contain sodium nitrite. Impregnatingbaths containing both the intermediate and sodium nitrite are used in anadvantageous modification of my dyeing process. When fabrics areimpregnated therewith the fabric contains both the intermediate and thesodium nitrite and a dyestuff is developed by treating with acidsolutions. The acid solution reacts with the sodium nitrite to diazotizethe intermediate. By adjusting the ratio of the sodium nitrite to theintermediate. the proportion of the intermediate which is diazotized andthe proportion of the intermediate which remains undiazotized andfunctions as an end component may be thus readily adjusted to controlthe dyeing of the fabric. When the acid solution contains acetic acid.sodium acetate is formed from the sodium nitrite and this isadvantageous. In this way the impregnated fabric contains two of theessential dye developing ingredients and the developing solution maycontain only the necessary acid. This modification may be advantageouslyused when the dyestufi is to be formed by acid coupling.

Also other soluble salts may be added to the impregnating baths toassist in the dyeing and these sometimes function to assist in fixingthe intermediate or the dyestuii on the fiber. For instance. a smallamount of ammonium chlorid may be added to the impregnating bath.

Also, the impregnating baths may contain small amounts of organicliquids, for instance, methyl alcohol may be added. About 50 cc ofmethyl alcohol may be added to 1 liter of the impregnating baths formedas described above.

When the impregnating bath is formed by dissolving a salt of theintermediate combined with an acid, such salt is usually dissolved inwarm water. For instance. the hydrochlorid salt of the intermediate maybe dissolved in warm water. The solution may be filtered if necessary toremove insoluble impurities and diluted to give the properconcentration. In certain dyeand ethers, for instance ing processes itis advantageous to use this type of impregnating bath. By applying theintermediate in the form of its saline combinations, in some cases andwith certain fibers the intermediate is advantageously fixed on thefiber. It may be that the intermediate in the form of a salt with acidhas the hydroxyl group in such a condition that it assists in fixing theintermediate on the fiber. Fabrics containing the hydrochlorid salt ofthe intermediate may have the dyestufi' developed in situ, by treatingthe impregnated fabric with suitable developing baths. If thesedeveloping baths contain salts of acids weaker than hydrochloric acid,they may react with the hydrochlorid, so that sodium chlorid and an acidderived from said salt are formed and assist in the dyeing process. Asalting out action may occur. Also in this modification, after thefabric has been impregnated with the hydrochlorid salt it may becarefullytreated to decompose said hydrochlorid salt and to precipitatethe free intermediate in situ in the fiber and thus assist in fixing itthereon. Also in this modification the developing bath may be insubstantially a neutralor very slightly acid condition and contain onlynitrous acid.

From the above. it will be clear to those skilled in the art thatvarious combinationsand modifications may be used in my process toadvantage in specific cases to obtain the most advantageous results.However, all of these modifications are within the generic scope of myinvention.

Fabrics and other materials which are to be dyed, may be impregnated invarious ways with these impregnating baths. Fabrics. yarns or loosefibers may be used. All types of textile materials may .beadvantageously treated in my processes. Natural and artificial fibersmay be used. Animal fibers, such as silk and wool. may be dyed by theprocesses herein disclosed. Suitable adjustments may be made in specificdetails for the natural characteristics of these animal fibers. Likewisevegetable fiber such as cotton. etc., may also be used making similaradjustments. Artificial fibers such as cellulose esters nitro andacetyl-cellulose and the regenerated cellulose materials, for instancerayon; likewise may be advantageously dyed in my processes. Each ofthese types of materials has certain characteristic properties in dyeingand the various modifications of my processes may be selected and usedin view of these individual characteristics. Any of these materials maybe impregnated with the intermediate, with or without other ingredients,by treating them with the described impregnating bath. The material tobe dyed may be immersed in the impregnating bath until sufficient of theintermediate is absorbed and then the excess removed in a suitablemanner. The wet material may be wrung or squeezed to remove excess. Itmay be dried, if desired, by evaporating the water and other volatileiquids present. After the intermediate is fixed on the fiber, theimpregnated material may be carefully washed with suitable liquids.

The fabric may be immersed or dipped in a bath of a solution of theintermediate in dilute caustic soda solution until the fabric hasabsorbed the desired amount. It is not necessary to dry the impregnatingfabric which may be directly treated with a suitable developing bat Woen goods-may be immersed and soaked V for approximately one-half hour inan impregnating-bath of a dilute aqueous causticsodasolution containingTurkey red oil and the intermediate. The fabric may be wrung out lightlyfrom. time to time. The treatment is continued until the fabric absorbsthe desired amount of material. The bath may advantageously also containsmall amounts of ammonium chlorid and of methyl alcohol. In thisprocedure the intermediate is advantageously fixed on the fabric. Afabric may be immersed for about 5 seconds in abath of dilute aqueoussolution-of caustic soda containing the intermediate, Tu"key red oil andsodium nitrite. The wet fabric is wrung to about double its dry weightand then quickly and exactly dried. The impregnating fabric thusproduced contains in addition to the intermediate other ingredients,particularly sodium nitrite.

A fabric may be immersed in an impregnating bath of the hydrochloridsalt of the intermediate dissolved in warm water, the fabric being keptin contact until it has absorbed the desired amountof the intermediate.If the intermediate is to be used in its free (insoluble) state, itsretention by the fiber may be increased by carefully decomposing thehydrochlorid .salt in 'situ. It is advantageous to form the dyestufi' bytreating the impregnated fiber with certain developing baths.

In some cases the material obtained from the impregnating step is in ain other cases it is in a moist or wet condition. The exact compositionof the developing bath and the manner in which it applies depend uponthe results desired and .upon the prior treatment in the impregnatingstep.

Diazotizing baths may be produced in various ways. One such diazotizingbath which may be generally used can be prepared by dissolving asuitable amount of sodium nitrite in about a liter of water at 0 0..adding sufficient hydrochloric acid and sodium acetate to give asolution with a neutral reaction to.Congo red indicator. Thisdiazotizing bath acts in effect like a solution of pure nitrous acid.The bath may also advantageously contain a certain amount offormaldehyde.

Another type of diazotizing bath may be made by dissolving a suitableamount of glacial acetic acid and sodium nitrite in water. To this typeof bath there may be also added a certain amount of commercial formalinor of methyl alcohol. A third type of diazotizing bath which may beadvantageously used with .materials impregnated dry condition, whilewith both the intermediate compound and sodium 'which'have been noted insome cases when the dyed materials have been treated with soapsolutions.

diazotizing bath and the dyestuff developed and fixed in situ, the dyedmaterial may be further processed to give the final product. It may berinsed with Water, worked in dilute soda or soap solutions, again rinsedwith pure water and dried. When treated with soap solutions, that issoaped, the dyed material may be ,revivified with acidu- After thematerial has been removed from thelated wash water before the finalrinsing and dyeing. Clear water acidified with about 2 per cent aceticacid may be advantageously used.

One of the advantages of certain modifications of my generic process isthat the material to be dyed is impregnated with a single dyestuffintermediate and the impregnated material treated with a simplediazotizing bath, whereby the dyestulT is simultaneously developed andcoupled in situ to produce the dyed material.

The following examples illustrate certain typical applications of mygeneric process. These examples do not limit the generic scope of myinvention. The parts are given by weight; mol" being a gram-molecule. 4

The examples illustrate various methods of preparing my new intermediatecompound.

Example I.-1 mol of meta-nitro-anilide of 2:3-hydroxy-naphthoic 21 :idis suspended in 1 liter oi water and heated to 60-65 C. Afterwards thereis added with agitation 390 grams of a 61 per cent solution of sodiumsulphide. The aminoanilide passes into solution and after termination ofthe reduction, the solution is filtered from inipurities. From thefiltrate the amino-anilide is precipitated by means or acid. Mineral oracetic acid may be used; such acid being added. until the solution isneutral to litmus. The amino-anilide is recovered, washed and dried. Inplace of the meta-nitro-anilide of 2:3-hydroxynaphthoic acid used in theabove example, there may be substituted the meta-nitro-toluidide of thesame acid.

Example 2.1 mol of meta-phenylene-diamine is carefully mixed with onemol of 2:3-hydroxynaphthoic acid and the mixture suspended in 600 gramsof toluene. The suspension in toluene is heated to C. and 12 grams ofPClz slowly added. The temperature is raised to the boiling point oftoluene and the excess of hydrochloric acid boiled off. After theseparation of this excess, the mixture is neutralized with sodiumcarbonate solution and the toluene distilled off. The solid residue ismixed with hot water and boiled to extract soluble impurities. stuff andthis then dried and ground.

In place of the meta-phenylenediamine in the above example there may besubstituted metatoluylene diamine.

Example 3.-1 mol of salicylic acid is condensed with 1 mol ofmeta-nitroaniline in a manner similar to that of Example 1. Themeta-nitroanilide thus obtained is reduced by the process set forth inExample 1.

Example 4.-1 mol of benzidine is mixed with 1 mol of salicylic acid andcondensation is eiiected in a manner similar to that set forth inExample itated by means of acid; the acid being in sufiicient amount toproduce substantial neutrality.

Example 5.1 mol of 1-phenyl-5-pyrazolone-' 3-carboxylic acid iscondensed with 1 mol of metanitro-aniline in the same manner as setforth in Example 2. The nitro-aniline thus produced is then reduced tothe corresponding amino compound by the method of Example 1.

Example 6.-1 mol of meta-nitro-benzoic acid with 1 mol of meta-nitroaniline and condensation effected by the method of Example 2. Thedinitroanilide thus produced is reduced by the process of Example 1using a double quantity of The solution is filtered from the dyethereducing agent. The dinitro-anilide is suspended in 2 liters of water at-70" C. and either grams of 61 per cent sodium sulphide solution or analkaline solution of stannous oxid in equivalent quantity is added.After reduction, the reaction product is acidified with suflicientsulfuric acid to give a strong acid reaction. The intermediate isrecovered by filtration and dried. Before being used in the dyeingprocess the dried product is extracted with dilute caustic sodasolution. and then dissolved in hydrochloric acid solution. the acidcontent of which is suflicient to give a slightly acid reaction.

Example 7.-1 mol of meta-phenyleneor meta-toluylene-diamine isintimately mixed with 1 mol of beta-hydroxynaphthoic acid and themixture suspended in 600 grams of toluene. This suspension in toluene isslowly added to a mixture comprising 60 grams of phosphorus trichloridand 60 grams of toluene maintained at 50 or 60 C. The reaction mixturethus obtainedlisbrought to a temperature corresponding to the boilingpoint of toluene and maintained at this temperature until the excess ofhydrochloric acid is driven off. The remaining liquid is neutralizedwith aqueous soda solution and the toluene removed by steamdistillation. The residue after distillation is poured into 2V liters ofhot water and boiled and the solution thus obtained filtered to separatethe intermediate from the soluble impurities. Then it is dried andground.

Example 8.l mol of dianisidine as the free base is dissolved in 600 cc.of chlorobenzol. 1 mol of freshly made beta-hydroxynaphthoic acidchlorid is dissolved in toluene and slowly added with constant stirringto the chlorbenzol solution of dianisidine. After the reaction iscomplete the' condensation is recovered and purified in a manner similarto that set forth in Example 4.

The following examples are typical processes of the impregnating anddyeing of fabrics by means of my new intermediates.

Example 9.-An impregnating bath is prepared by dissolving 20 grams ofmeta-aminoanilide of '2:3 hydroxynaphthoic acid in 200 cc of watercontaining 25 cc of 10" B. caustic soda solution and then heating thesolution until it'becomes clear. This clear solution is diluted withcold water to 1 liter. A fabric of cotton, wool or artificial fiber issaturated with this impregnating solution. The impregnated fabric istreated with a diluted aqueous solution of acetic acid'to neutralize orslightly acidify the same. It is then introduced into a diazotizingsolution. This diazotizing solution may be prepared by dissolving 7grams of sodium nitrite in a liter of water acidified with 20 cc of percent acetic acid. By submerging the impregnated fabric for a few minutesin the above developing bath the dyestufi' is developed in situ and thefabric is dyed a splendid red shade. The dyed fabric may be washed anddried in any suitable manner.

Example 10.An impregnating bath is prepared by dissolving 20 grams ofthe hydrochlorid of meta-amino anilide of meta-aminobenzoic acidproduced as in Example 6, in 1 liter of warm water. Fabric is saturatedwith this impregnating solution. The saturated fabric is then treatedwith a diazotizing solution containing 7 grams of sodium nitrite in aliter of water acidified by means of 20 cc in water of acetic acid. thesolution being rendered neutral to Congo red by the addition of sodiumacetate. In a few minutes the dyestuif is developed in situ and thefabric is dyed a brownish yellow shade.

Example 11.-An impregnating bath may be prepared as follows: 20 grams ofmeta-aminoanilide of 2:3 hydroxynaphthoic acid are mixed with 7.5 gramsof Turkey red oil to obtain an intimate mixture. The mixture is added toabout 200 cc of hot water (80 to 90 C.) and 30 cc of caustic sodasolution of 40 B. The solution thus obtained is then mixed with 500 ccof cold water containing dissolved therein 30 grams of solid 97 per centnitrite and heated to obtain'a clear solution. After cooling the clearsolution is diluted with cold water to about 1 liter.

Fabric is submerged in this impregnating bath for about 5 seconds,removed and wrung to about double its dry weight, and then quickly andexactly dried. The dried fabric is treated with a suitable diazotizingbath. A suitable diazotizing bath may be prepared by mixing together tocc of hydrochloric acid of 19-20 B., 50 cc of alcohol and cc of 35 percent formalin solution. With this particular diazotizing bath theimpregnated fabric should be submerged therein for about 20.to 30seconds. The treated fabric is removed from the diazotizing bath, wrungout and thensubmerged in a 1 per cent soda solution for about 2 minutes.It may be subsequently boiled in a soap solution for about 15 minutes,and then rinsed with water. After rinsing with water the dyed fabric maybe revivified by treating with slightly acidified water, containingabout 2 per cent acetic acid. After revivification the fabric is rinsedand dried. The fabric is dyed in a scarlet red shade.

The above-process may. be used with other in-, termediate compounds ofthe generic class set forth. The following table gives certain typicalintermediates with the colors produced:

Benzidine-mono-salicylid Yellow Dianisidin-mono-hyclroxynaphthosid-Heliotrope Meta-amino-ortho toluidid of beta Para-amino-cresol methyletheranilid of 2:3 beta hydroxynaphthoic acid Dark blue (approximatelyequal to Chicago blue R4) Example 12.-An impregnated bath may beprepared as follows: 2 grams of meta-aminoanilide of 2:3 betahydroxynaphthoic acid is mixed with 7.5 grams of Turkey red oil until anintimate mixture is obtained. The mixture is dissolved in 200 cc of hotwater at 80 to 90 C., and about 30 cc of caustic soda solution of 40 B.This solution is diluted with cold water to about 1 liter.-

The fabric is dipped in.the above impregnating bath until it issufficiently impregnated and then removed. The moist impregnated fabricis directly introduced into a suitable diazotizing and developing bath.Such a suitable bath maybe prepared by mixing together 20 cc of glacialacetic acid, 20 grams of solid nitrite, cc of 33 per cent formalin andsuflicient water to make about a liter of solution. The impregnatedfabric may be submerged for about 15 to 20 minutes in said impregnatingbath and then removed and rinsed with water. During such treatment thedyestuff is produced by simultaneous'diazotization and coupling toproduce the dyed fabric. After rinsing with water the dyed product maybe then washed with weak soda or soap solution. When soap solution isused the dyed fabric may be revivifled or quickened with slightlyacidulated water as disclosed in Example 11. This treatment gives asomewhat better shade to the dyed fabric.

In the above process, other of my new intermediates may be substitutedfor the particular meta-aminoanilide given above. However, when theamino group in such compounds is in the para position, the processshould be slightly modified. With the amino group in the para position alonger time is required to complete the coupling. The coupling may befacilitated by treating the fabric, after removing it from thediazotizing bath and before washing, with dilute soda or ammoniasolution. With di-anisidine-mono-naphthosid, heliotrope colors areobtained, but such colors require a rather long treatment with the weakoda or ammonia solution to properly develop them. This modificationshould be used in certain cases, for otherwise a subsequent treatmentwith soap solution may have an undesirable effect upon the dyedmaterial. With fabric dyed with dianisidine amino hydroxynaphthosid, ifthe treatment with soda or ammonia solution is not sufficient, thesedyed fabrics when soaped develop brown shades. It seems that these brownshades are caused by brown products formed by acid coupling.

Example 13.The fabrics impregnated by the process of Example 12, may bedeveloped with diazotizing baths somewhat different from that given inExample 12. For instance they may be treated with a diazotizing bathmade as follows: Dissolve 20 grams of nitrite in 1 liter of Water at 0"C. and add to the solution thus obtained 20 cc of hydrochloric acid of20 B. and 50 cc of commercial formalin solution; then add sufficientsodium acetate until the solution has a neutral reaction to Congo redindicator. This diazotizing bath behaves like a pure nitrous acidsolution. The impregnated fabric is submerged in such diazotizing bathfor a suitable length of time to produce the dyed fabric and thenremoved. The dyed fabric may be further processed as disclosed in eitherExample 11 or 12.

Example 14.An impregnating bath may be prepared as follows:-5 grams ofmeta-aminoanilide of 2:3 beta-hydroxynapthoic acid are mixed with 2grams of Turkey red oil and the mixture added to about 200 cc of hotwater containing 3 cc of 30 B. soda lye. The solution is heated untilclarified. 1 gram of ammonium chlorid is added and the solution heatedfor several minutes to boiling. It is then diluted with cold watercontaining about 50 cc of methyl alcohol per liter.

Woolen fabric is soaked in the above impregnating solution for about ahalf hour. During this time the fabric may be removed, lightly wrung outand returned to the bath; thus insuring a thorough impregnation of thematerial. After the impregnation is sufficient, the fabric is removedand lightly wrung out, and then wound on suitable apparatus tofacilitate the mechanical handling of the material. The impregnatedfabric is then ready to be treated with the diazotizing bath. A suitablediazotizing bath comprises an aqueous solution containing 5 grams ofsodium nitrite, 5 cc of glacial acetic acid and 20 cc of methyl alcoholper liter. The impregnated fabric is submerged in the above diazotizingbath. About 45 to minutes is usually sufficient for diazotization andself-coupling. The

wherein R1 represents an aryl residue of the class consisting of benzeneand naphthalene nuclei, or the residue of the enol component of aketocarboxylic acid and R2 represents an aryl residue of the classconsisting of benzene and diphenyl nuclei, treating the so impregnatedfabric with a diazotizing solution to diazotize and self-couple the saidintermediate and form in situ the azo dyestufi thereby producingdirectly the dyed fabric.

2. In the manufacture of dyed fabrics containing animal, vegetable orartificial fibers, the

process which comprises impregnating such fabric with a solution of anamino compound of the anilide type having the probable formula:

(J-N-RrNH:

0 11 wherein R2 represents an aryl residue of the class consisting ofbenzene and diphenyl nuclei, treating the so-impregnated fabric with adiazotizing solution to diazotize and self-couple the said intermediateand form in situ the azo dyestuff thereby producing directly the dyedfabric.

3. In the manufacture of dyed fabrics containing animal, vegetable orartificial fibers, the process which comprises impregnating such fabricwith a solution of an amino compound of the anilide type having theprobable formula:

wherein R2 represents an aryl residue of the class consisting of benzeneand diphenyl nuclei, treating the so impregnated fabric with adiazotizing solution to diazotize and self-couple the said intermediateand form in situ the azo dyestuif thereby producing directly the dyedfabric.

l. In the manufacture of dyed fabrics containing animal, vegetable orartificial fibers, the process which comprises impregnating such fabricwith a solution of an amino compound of the anilide typehaving theprobable formula:

wherein R2 represents an aryl residue of the class consisting of benzeneand diphenyl nuclei and R4 represents hydrogen or an alkyl group,treating the so impregnated fabric with a diazotizing solution todiazotize and self-couple the said intermediate and form in situ the azodyestuff, thereby producing directly the dyed fabric.

5. In the manufacture of dyed fabrics containing animal, vegetable orartificial fibers, the proc ess which comprises impregnating such fabricwith a solution of an amino compound of the anilide type having theprobable formula:

wherein R2 represents an aryl residue of the class consisting of benzeneand diphenyl nuclei, R6 represents aryl or alkyl group, treating the soimpregnated fabric with a diazotizing solution to diazotize and self-couple the said intermediate and form in situ the azo dyestuff, therebyproducing directly the dyed fabric.

6. In the manufacture of dyed fabrics containing animal, vegetable orartificial fibers, the process which comprises impregnating such fabricwith a solution of an amino compound of the anilide type having theprobable formula:

wherein R1 represents an aryl of the class consisting of benzene andnaphthalene nuclei, residue or the residue of the enol form of aketocarboxyl acid, R represents an aryl residue of the class consistingof benzene and diphenyl nuclei, and X represents OH or NHz groups, andin which at least one X is NH2, treating the so impregnated fabric witha diazotizing solution to diazotize and self -couple the saidintermediate and form in situ the azo dyestuff thereby producingdirectly the dyed fabric.

'7. In the manufacture of dyed fabrics containing animal, vegetable orartificial fibers, the process which comprises impregnating such fabricwith a solution of an amino compound of the anilide type having theprobable formula:

wherein R1 represents an aryl of the class conwherein R1 represents anaryl group of the class consisting of benzene and naphthalene nuclei orthe residue of the enol form of a ketocarboxylic acid, and R4 representshydrogen or an alkyl group, treating the so impregnated fabric with adiazotlzing solution to diazotize and self-couple the said intermediateand form in situ the azo dyes tufi, thereby producing directly the dyedfabric.

9; In the manufacture of dyed fabrics containing animal, vegetable orartificial fibers, the process which comprises impregnating such fabricwith a solution of an amino compound of the anilide type having theprobable formula:

wherein R1 represents a benzene or naphthalene residue, R2 represents anaryl residue of the class consisting of benzene and diphenyl. nuclei,and X represents a OH or NHz group, treating the so impregnated fabricwith a'diazotizing solution to diazotize and self-couple the saidintermediate and form in situ the azo dyestuff, thereby producingdirectly the dyed fabric.

10. In the manufacture of dyed fabrics containing animal, vegetable orartificial fibers, the process which involves the step of impregnatingsuch fabric with a solution of an amino compound of the anilide typehaving the probable formula:

X- li -N --n--x I l (1 wherein R represents an aryl residue of the classconsisting of benzene. naphthalene and diphenyl nuclei and X representsOH, or NH; groups and in which at least one X is NH2.

11. In the manufacture of dyed fabrics containing animal, vegetable orartificial fibers, the process which involves the step of impregnatingsuch fabric with a solution of an amino compound of the anilide typehaving the probable formula:

in u I 1 now in NH 3% 1'1 wherein R2 represents an aryl residue of theclass consisting of benzene and diphenyl nuclei, R4 represents hydrogenor an alkyl group.

12. In the manufacture of dyed fabrics containing animal, vegetable orartificial fibers, the process which involves the step of impregnatingsuch fabric with a solution of an amino compound of the anilide typehaving the probable formula:

wherein R1 represents an aryl residue of the class consisting of benzeneand naphthalene nuclei, or the residue of the enol form of aketocarboxylic acid, and R2 represents an aryl residue of the classconsisting of benzene and diphenyl nuclei.

13. In the manufacture of dyed fabrics containing animal, vegetable orartificial fibers, the process which involves the step of impregnatingsuch fabric with a solution of an amino compound of the anilide typehaving the probable formula:

' wherein R1 represents a benezene or naphthalene compound in the freestate having the probable formula:

no u. x in Nil-.

wherein R1 represents a benzene or naphthalene residue, and R2represents an aryl residue of the class consisting of benzene anddiphenyl nuclei, treating the so-impregnated fabric with a diazotizingsolution to diazotize and self-couple said intermediate and form in situan azo dyestuff and thereby producing directly the dyed fabric.

15. The process of claim 14 wherein said salt of said amino compound isdecomposed to regenerate in situ the said amino compound prior totreating with the said diazotizing solution.

16. In the manufacture of dyed fabric containing animal, vegetable orartificial fibers, the process which comprises impregnating such fabricwith an aqueous alkaline solution of an amino compound of the anilidetype. said amino comwherein R1 represents a benzene or naphthaleneresidue, and R2 represents an aryl residue of the class consisting ofbenzene and diphenyl nuclei, treating the so-irnpregnated fabric with adilute acid solution to form in situ the said amino compound in the freestate, and then applying to the so-treated fabric a diazotizing solutionto diazo tize and self-couple said intermediate and form insitu an azodyestuff and thereby producing directly the dyed fabric.

17. In the manufacture of dyed fabric containing animal, vegetable orartificial fibers, the process which comprises impregnating such fabricwith an aqueous solution comprising an amino compound of the anilidetype, caustic soda, sodium nitrite and water, said amino compound havingthe probable formula:

wherein R represents an aryl residue of the class consisting of benzene,naphthalene and diphenyl nuclei or the residue of the enol form of aketocarboxylic acid, and X represents OH or NHz groups and in which atleast one X is NHz and wherein R represents an aryl residue of the classconsisting of benzene, naphthalene and diphenyl nuclei or the residue ofthe enol form of a ketccarboxylic acid, and, X represents OH or NH:groups and in which at least one X is NI-Iz and at least one R is suchan aryl residue, treating the so impregnated fabric with a diazotizingsolution to diazotize and self-couple said intermediate and iii) form insitu the azo compound and thereby producing directly the dyed fabric.

19. In the manufacture of dyed fabric containing animal, vegetable orartificial fibers, the process which comprises impregnating such fabricwith an aqueous solution comprising an amino compound of the anilide typcaustic soda, Turkey red oil and water, said amino compound having theprobable formula:-

wherein R represents anaryl residue of the class consisting of benzene,naphthalene and diphenyl nuclei or the residue of the enol form of aketocarboxylic acid, and X represents OH or NH: groups and in which atleast one X is NH; and at least one R is such an aryl residue, treatingthe so impregnated fabric with a diazotizing solution to diazotize andself-couple said intermediate and form in situ the azo compound andthereby producing directly the dyed fabric.

20. In the manufacture of dyed fabric containing animal. vegetable orartificial fibers, the process which comprises impregnating such fabricwith an aqueous solution comprising an amino compound of the anilidetype, caustic soda, an alcohol and water, said amino compound having theprobable formula:

X-Jn-( N-R-X i i wherein R represents an aryl residue of the classconsisting of benzene, naphthalene and diphenyl nuclei or the residue ofthe enol form of a ketccarboxylic acid, and X represents OH or NH:groups and in which at least one X is NR1; and at least one R is such anaryl residue, treating the so impregnated fabric with a diazotizingsolution to diazotize and self-couple said intermediate and form in situthe azo compound and thereby producing directly the dyed fabric.

21. In the manufacture of dyed fabric containing animal, vegetable orartificial fibers, the process which comprises impregnating such fabricwith an aqueous solution comprising an amino compound of the anilidetype, caustic soda, ammonium chloride and water, said amino compoundhaving the probable formula:

wherein R represents an aryl residue of the class consisting of benzene,naphthalene and diphenyl nuclei or the residue of the enol form of aketccarboxylic acid, and X represents OH or NH: groups and in which atleast one X is NH: and at least one R is such an aryl residue, treatingthe so impregnated fabric with a diazotizing solution to diazotize andself-couple said intermediate and form in situ the azo compound andthereby producing directly the dyed fabric.

22. In the manufacture of dyed fabric containing animal, vegetable orartificial fibers, the

process which comprises impregnating such fabric with an aqueoussolution of the hydrochlorid type salt of an amino compound, said aminocompound being of the anilide type and having the probable formula:

wherein R represents an aryl residue of the class consisting of benzene.naphthalene and diphenyl nuclei or the residue of the enol form of theketocarboxylic acid and X represents OH or NH: grzoups and in which atleast one X is NH: and at least one R'iis such an aryl residue, treatingthe so impregnated fabric with a diazotizing solution to diazotize andself -couple said intermediate and form in situ an azo dyestuff andthereby producing. directly the dyed fabric.

23. The process of claim 22 wherein the impregnated fabric before beingtreated with the diazotizing solution is treated with a dilute alkalinesolution to decompose said salt of the hydrochlorid type and form insitu in the fabric said amino compound.

24. In the manufacture of dyed fabric containing animal, vegetable orartificial fibers, the process which comprises impregnating such fabricwith an aqueous solution comprising an amino compound of the anilidetype having the probable formula:

wherein R represents an aryl residue of the class consisting of benzene,naphthalene and diphenyl nuclei or the residue of the enol form of aketocarboxylic acid, and X represents OH or NHz groups and in which atleast one K is NH: and at least one R is such an aryl residue, treatingthe so impregnated fabric with a diazotizing solution comprising anacid, sodium nitrite, an alcohol and water to diazotize and self-couplesaid intermediate and form in situ an azo compound and thereby producingdirectly the dyed fabric,

25. In the manufacture of dyed fabric containing animal. vegetable orartificial fibers, the process which comprises impregnating such fabricwith an aqueous solution comprising an amino compound of the anilidetype having the probable formula:

wherein R represents an aryl residue of the class consisting of benzene,naphthalene and diphenyl nuclei or the residue of the enol form of alretocarboxylic acid. and X represents OH or NH: groups and in which atleast one X is NHz and at least'one R is such an aryl residue and water,treating the so impregnated fabric with a diazotizing solutioncomprising an acid, sodium nitrite, formaldehyde and water to diazotizeand self-couple said intermediate and form in situ an azo compound andthereby producing directly the dyed fabric.

26. In the manufacture of dyed fabric containing animal, vegetable orartificial fibers, the process which comprises impregnating such fabricwith an aqueous solution comprising an amino compound of the anilidetype having the probable formula:

wherein R. represents an aryl residue of the class consisting ofbenzene, naphthalene and diphenyl nuclei or the residue of the enol formof a ketccarboxylic acid, and X represents OH or NH: groups and in whichat least one X is NH: and at least one R. is such an aryl residue, andtreating the so impregnated fabric with a diazctiz ing solutioncomprising an acid, sodium nitrite, sodium acetate and water todiazotize and selfcouple said intermediate and form in situ the azocompound and thereby producing directly the dyed fabric, the amount ofsodium acetate beconsisting of benzene, naphthalene and dlphenyl ingsuflicient to render the diazotizing solution nuclei or a residue of'theenol form of a ketoneutral to Congo red indicator. carboxylic acid and Xrepresents OH or NH2 27. In the manufacture of dyed fabric containgroupsand in which at least one X is NH: and

5 ing animal, vegetable or artificial fibers, the procat least one B. issuch an aryl residue, treating 80 ess which comprises impregnating suchfabric the so impregnatedfabric with a diazotizing so- I with a aqueoussolution comprising an amino lution comprising hydrochloric acid,alcohol, forhaving the probable formula:

compound of the anilide type, caustic soda, somaldehyde and water todiazotize and self-couple dium nitrite and water, said amino compoundsaid intermediate to form in situ the azo dyestutf and thereby producedirectly the dyed fab- XR---CNRx JOSEPH FELIX TURSKL wherein Rrepresents an aryl residue of the class CERTIFICATE or connection.

intent No. 1,922,463. 7 August 15, 193}.

JOSEPH FELIX TURSKI.

It is hereby certified that error appears in the printed specificationoi the above numbered patent requiring correction as follows: Page i,ime 14, strike out the article "a" first occurrence; page 6, lines 104and 105, and 125 and --12 6. claims 6 and7, respectively, strike out theword "residue" and insert the some after "aryi" in lines 103 and 124. ofsaid claims; and that the said Letters-Pet en: should be read with thesecorrections therein that the same may conform to the record of the casein the Patent Oiiice. I I

Signed and settled this 14th day of November, A. D. 1933.

in M. Hopkins (Seal) .Aeting Commissioner oiv Patents.

